Über die Oxydationsprodukte von Thiocarbonsäureamiden, XVI. Oxydationsreaktionen an Thiocarbonsäureamiden mit elektronenanziehenden Substituenten am C‐Atom

Abstract

Ist das C‐Atom der Thioamidgruppe mit einem elektronenanziehenden Rest verknüpft, so entstehen nur dann stabile S‐Oxide, wenn eine unsubstituierte oder allenfalls eine mono‐ substituierte Thioamidgruppe vorliegt. Im letzteren Falle müssen Einflüsse wirksam sein, welche den Elektronenbedarf am C‐Atom der Thioamidgruppe vermindern.

Synthesis, characterization, and derivatization of some novel types of fluorinated mono- and bis-imidazolidineiminothiones with antitumor, antiviral, antibacterial, and antifungal activities

“…Thus, commercial isocyanates 5a-g with various aromatic substituents (p-tolyl, p-methoxyphenyl, p-thiomethylphenyl, benzyl, p-chlorophenyl, 3,5-dichlorophenyl, and 2,4,5-trichlorophenyl) were reacted with an equimolar amount of p-fluorocyanothioformanilide (4) in ether in the presence of a few drops of triethylamine as a catalyst to furnish the corresponding 5-imino-4-thioxo-2-imidazolidinones 6a-g as shown in Scheme 2. p-Fluorocyanothioformanilide (4) was prepared by treating an ethanolic solution of commercial 4-fluorophenyl isothiocyanate with an aqueous solution of KCN according to literature protocols [10][11][12][13][14][15][16][17][18][19]. The ring closing reaction proceeded by attack of the nitrogen atom of the cyanothioformanilide onto the isocyanate carbon, where the ensuing annulation proceeds by attack of the resulting nitrogen anion onto the electrophilic nitrile group.…”

“…The nitrile function serves as an electrophilic center and may participate in subsequent reactions. These properties have been exploited in the development of a variety of ''one-pot'' A series of thirty eight novel imidazolidineiminothiones (6a-g, 10a-h, 13a,b, 15a-d, and 16a), 5-thioxoimidazolidine-2,4-diones (7a-d, 11a-e, 14a,b, and 16b), and bis-imidazolidineiminothiones (17)(18)(19)(20) with various fluorinated aromatic substituents at N- (1) and N-( 3) were prepared in 75-85% yields. The imidazolidineiminothiones were synthesized from fluorinated N-arylcyanothioformanilides and substituted aromatic isocyanates, and by the reactions of fluorinated aromatic isocyanates with fluorinated and non-fluorinated aromatic N-arylcyanothioformanilides.…”

“…These have been earlier prepared by treating N-aryl isothiocyanates with cyanide [10][11][12][13][14][15][16][17][18][19] and by other classical methods [20]. Recent approaches have employed environmentally-friendly N-arylimino-1,2,3-dithiazoles which transform readily to the corresponding cyanothioformanilides under various conditions [21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36].…”

“…ring-closure reactions of N-arylcyanothioformanilides [13,18,42,[46][47][48] to yield various heterocyclic cores which include pyrroles [14,[49][50][51], pyrrolothiazoles [52], imidazoles [10,13,[53][54][55][56][57][58][59][60][61], benzimidazoles [62], oxazoles [11,43,47,48], benzoxazoles [43,47,48,62], thiazoles [52,63], quinazolinonethiones [42,60], quinoxaline [42], imidazoquinoxalines [63,64], among others [65][66][67][68][69][70][71].…”

A comparative study of the behavior of cyanothioformamide and oxazolidine (thiones or iminothiones) towards some binucleophiles

“…Cyanothioformamides (I) [1,2] have been used widely for syntheses of heterocyclic compounds, such as imidazoles [3], oxazoles [4], and thiazoles [5,6]. Our program on ring-closure reactions [7], activated nitriles [8], and the chemistry of cyanothioformamides [9][10][11][12] led us to react I with chalcones, maleimides, and acetylenedicarboxylic acid to give the corresponding pyrroles [13].…”